3-acylamido-5-(m-sulfobenzoyloxy) pyrazole coupler compounds



United States Patent 0 3-ACYLAMIDO-S-(M-SULFOBENZOYLOXY) PYRAZOLE COUPLER COMPOUNDS llmari F. Salminen, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application December 4, 1952, Serial No. 324,153

9 Claims. (Cl. 95-6) No Drawing.

quirements of subtractive color photography, that is, dyes Y which are colored yellow, magenta or blue-green and many have been directed to methods for rendering the couplers non-diffusing in the silver halide emulsion. .A number of other patents pertain to providing coupler compounds with alkali solubilizing groups such as sulfonic acid groups which facilitate the incorporation of the coupler compounds into aqueous silver halide emulsions without destroying the non-diffusing properties of the couplers.

I have discovered that solubilizing groups can be introduced into pyrazolone coupler molecules in an unexpected manner to facilitate incorporation of the couplers into aqueous systems and that the solubilizing groups of such couplers are readily eliminated during color development to yield relatively insoluble dye images and therefore improved image sharpness. Moreover, the coupling activity of the couplers is surprisingly great considering the manner of attachment of the solubilizing group to the pyrazolone coupler molecule. In contrast to this behavior of the coupler compounds of the invcntion, similar coupler compounds containing the reactive methylene group and the same solubilizing group do not possess the increased coupler activity as will be explained more fully hereinafter.

One object of my invention is to provide coupler compounds containing alkali solubilizing groups, which groups are readily removable during color development. Another object is to provide coupler compounds which have increased coupling activity. Other objects will become apparent from consideration of the following description of my invention.

The coupler compounds of the invention are 5-pyrazole derivatives and possess the following structural formula:

N=CNHC OR in which R represents a mononuclear aryl group of the benzene series substituted or not, such as phenyl, trichlorophenyl, etc., and R represents either a mononuclear aralkyl group of the benzene series, a mononuclear aryloxyalkyl group of the benzene series, or a mononuclear arylene group, such as a phenoxypropyl group or a phenoxyacetamidophenyl group. The presence of the rn-sulfobenzoyl substituent in the 5-position of the pyrazole nucleus will be noted. It is believed that the presence of this group in the 5-position together with the acylamido group in the 3-position of the molecule is responsible for the improved coupling rates of the couplers compared to simple S-pyrazolone or 3-acyl amido-S-pyrazolone coupler compounds. The nature of the interactivity of the substituents in the 3- and 5-posi tions of the pyrazole coupler molecule is not understood.

The following examples illustrate the coupler compounds of my invention.

1 =0 NH0 0 s u NHO ocmo-Qmnm 1 c=on S OaH-N I 0 3 1- (2,4,6-trichlorophenyl;-3-{m- [a- 2,4-di-tert-amylphenoxv acetamidolbenzamido -5-m-sulfobenzoxy pyrazole pyridinium salt 1-phenyl-3-(m-[a- (2,4-di-tert-amylphenoxy) acetamido1benzamido}5-m-sulfobenzoxy pyrazole pyridinium salt NHCOCHlO-Q-Csliii SOsH-N l-[p (p tert butylphenoxy)phenyl]- 3-[a-(p-tert-butylph en 0x1; -propi0namido] -5-m-sulfobenzoxy pyrazole pyridinium sa 1-pl1enyl-3-m- ['y- (2,4-di-tert-amylphenoxy hutyramido 1 benzarn1do-5-m-su1f0benzoxy pyrazole pyridimum salt C=CH l-[p (p tert butylphenoxy)pheny1]-3- ['y-(2,4-di-tert-a mylphenoxl pbutyramido]-5-m-sulfobenzoxy pyrazole pyridinrum sa The coupler compounds of the invention are also unique, particularly in regard to their method of preparation. The coupler compounds are prepared by reacting m-chlorosulfonyl benzoic acid with 3-acylamido-5-pyrazolones in the presence of pyridine. Surprisingly, the result is that the carboxyl group of the sulfonyl halide rather than the chlorosulfonyl group reacts with the enolized carbonyl group of the pyrazolone. Little is known of the reactions of m-chlorosulfonyl benzoic acid. However, the unexpected nature of this reaction is attested by the prior knowledge in a similar reaction (Sekera and Marvel, J. A. C. S. 55, 345 (1933)) showing that aromatic sulfonyl halides'form esters with alcohols in the presence of pyridine. Also, Re, Annalen 233, 228, has shown that a similar compound, sulfophthalic acid reacts with ammonia at the sulfo group.

Coupler 1 is prepared as follows: In a suitable 3-necked flask equipped with a thermometer, a coil condenser, a stirrer and stoppered with a calcium chloride tube, are placed volumes of pyridine and while stirring vigorously, 11.53 parts of m-chlorosulfonyl benzoic acid are added. A rise in temperature is noted from 29-52 C. and the solution turns yellow. Stirring is continued for 1 /2 hours and at this time there are added 34.5 parts of 1 (2,4,6-trichlorophenyl) 3 {m [oz-(2,4-di-tert-amy1- phenoxy)acetamidolbenzamido} 5 pyrazolone (U. S. Patent 2,600,788, Example No. 7). The solution is complete within 30 minutes and a change of color to deep purple is evident. Stirring is continued overnight. The viscous resulting solution is poured with stirring upon 600 parts of ice in which 160 volumes of concentrated hydrochloric acid have been added. After one-half hour of stirring, the white product is filtered and washed well with several portions of Water and dried as much as possible upon the filter. The moist material is then dried at C. 41.5 parts of coupler are obtained which represents an 86.5 percent yield of the theoretical quantity of 48 parts.

Coupler 2 is prepared as follows: In a suitable 3- necked flask provided with a stirrer and thermometer is I NHC oomornomog-ctnn l s n N=(J-NHC oom-Qmao oomoQ-oaau C b ll placed 25 volumes of pyridine, to which is added 5 parts of m-chlorosulfonyl-benzoic acid. After 15 minutes, to the resulting mixture is added 5 parts of the pyrazolone, l phenyl 3 {m-[a-(2,4 di-tert-amylphenoxy)acetamido]benzarnido}-5-pyrazolone (prepared as Coupler No. 7 of U. S. Patent 2,600,788 except using aniline in place of 2,4,6-trichloroaniline). The reaction mixture is stirred for one hour at ordinary temperature, added in a thin stream to 300 parts of ice containing 50 volumes of concentrated hydrochloric acid. The solid which precipitates is filtered by suction, washed on the funnel with ice water in order to remove pyridine. The product is air-dried, 7 parts being obtained.

Coupler 3 is prepared as follows: In a suitable flask is dissolved in 2.2 parts 1-[p-(p-tert-butylphenoxy)phenyl]-3-[a (p tert-butylphenoxy)propionamido1-5-pyrazolone by warming with 25 volumes of benzene. To the solution is added 1 part of m-chlorosulfonylbenzoic acid, followed by 1.2 parts of pyridine. The solution becomes turbid and is heated under reflux for three hours. On cooling, the benzene is removed and the residue triturated with petroleum ether to a white solid; it is filtered, washed on the funnel with petroleum ether and dried, 2.3 parts being obtained. The pyrazolone coupler used in this synthesis is described in U. S. Patent 2,369,489, Example Coupler 4 is prepared as follows:

-(2,4-di-tert-amylphenoxy)butyric acid is first prepared as follows: In a suitable vessel provided with stirrer, thermometer, and coil condenser is placed 500 volumes of absolute methyl alcohol and 46 parts of sodium. To the sodium methoxide thus made is added 468 parts of 2,4-di-tcrt-amylphenol and stirred 15 minutes. Butyrolactone (198 parts) is added and the mixture refluxed 15 minutes. The condenser is inverted and the excess methyl alcohol distilled up to Concentrated hydrochloric acid (500 volumes) in 1400 volumes of distilled water is added continuously with stirring, and the acidic mixture poured into a glass tray to cool. The solid is washed and filtered, 650 parts being obtained. The

product is crystallized from 1500 volumes of ligroin, 300 grams of product melting at 98-100 being obtained.

-(2,4-di-tert-amylphenoxy)butyryl chloride is prepared as follows: In a suitable vessel, provided with a condenser, is placed 32 parts of y-(ZA-di-tert-amylphenoxy)butyric acid to which is added 22 volumes of thionyl chloride. The mixture is heated for 3 hours at 40; at the end of this time the excess thionyl chloride is removed under vacuum, the temperature being allowed to reach 55. The crude acid chloride is purified by distillation, B. P. 165166/ 1 mm.

l-phenyl-3-{3-l'y-(2A di tert amylphenoxy)butyramido]-benzamido)}-5-pyrazolone is prepared as follows: In a suitable reaction vessel, provided with a stirrer, thermometer, and dropping funnel, is placed 100 volumes of glacial acetic acid and 5 volumes of water. To this mixture is added 2.83 parts of anhydrous sodium acetate which is allowed to dissolve with stirring. 1-phenyl-3- (3-aminobenzamido)-5-pyrazolone, 8.3 parts, is added, and stirring continued 15 minutes to assure homogeneous distribution. After 15 minutes of stirring, 11.16 parts of -(2,4-di-tert-amylphenoxybutyryl) chloride is added in a slow stream in about 10 minutes with virgorous stirring. The mixture remains fluid for about 10 minutes after addition, and then sets up into a mush. It is allowed to stand 2 hours and then filtered free from the mother liquor, washed with 100 volumes of water to which 5 volumes of glacial acetic acid has been added, filtered and dried. The product is recrystallized from absolute alcohol; M. P. 218-220.

The desired coupler 4 is then finally prepared as follows: In a suitable reaction vessel, provided with a stirrer and thermometer, is placed parts of m-chlorosulfonylbenzoic acid followed by 175 volumes of pyridine. A clear solution results, with a rise in temperature. Within a few minutes a yellow solid separates. When the mixture has cooled to room temperature, 35 parts of the pyrazolone, prepared directly above, is added. Again the temperature rises. The mixture is stirred for approximately one hour at ordinary temperature, then added with stirring to a mixture of 350 volumes of concentrated hydrochloric acid in 1000 parts of ice.

The pale yellow mixture is filtered and the solid washed on the funnel with 2000 volumes of water containing 70 volumes of hydrochloric acid and free ice. The solid is dried at room temperature.

Coupler 5 is prepared as follows: In a suitable 3-necked flask provided with a stirrer and a thermometer is placed 5 parts of m-chlorosulfonylbenzoic acid, followed by 25 volumes of pyridine. After 15 minutes, to this mixture is added 5 parts of the 1-(2,4,6-trichlorophenyl)-3-{a-{p-[a- (2,4-di-tert-amy1phenoxy)acetamido]-phenyl}acetamido}- 5-pyrazolone (U. S. Patent 2,600,788). The reaction mixture is stirred for one-half hour, drowned by stirring in 300 parts of crushed ice containing volumes of concentrated hydrochloric acid. The cream-colored mixture is filtered by suction, the product washed on the funnel with water in order to remove pyridine, and the product air-dried, 6.2 parts being obtained.

Coupler 6 is prepared as follows: In a suitable 3-necked flask provided with a stirrer and a thermometer is placed 6.6 parts of m-chlorosulfonylbenzoic acid, followed by SOaH-N prepared by reaction of m-chlorosulfonylbenzoic acid with the appropriate methylene coupler give very useful dye images upon development in the presence of exposed silver halide with a primary aromatic amino silver halide developing agent, apparently by the same mechanism pointed out above; however, the coupling rates of these methylene couplers are markedly lower than those of the pyrazole couplers described above.

The coupler compounds of the invention may be incorporated into silver halide emulsions in the desired amount by merely dispersing the couplers in water and adding to the aqueous emulsion. Suitable silver halide emulsions are those well known in the art containing hydrophilic colloid vehicles such as gelatin, partially hydrolyzed cellulose esters, polyvinyl alcohol, etc. The emulsions containing the couplers may be employed for the production of colored photographic images on various supports such as glass, cellulose ester, or non-transparent reflecting medium such as paper or an opaque cellulose ester support. The emulsion containing the coupler compounds of the invention can be coated as one of several difierently sensitized silver halide emulsions on a support for the production of subtractively colored dye images, the emulsion containing the coupler of the invention pro viding the magenta dye image for the picture.

A suitable developer composition for use in development of exposed silver halide emulsions containing the coupler compounds of the invention is the following:

Grams 2-amino-5-diethyl-aminotoluene HCl 2 Sodium sulfite 5 Sodium carbonate 30 Water to 1 liter.

tioned, the coupling rate of the couplers is exceptionally high and can obviously be used to great advantage.

The aromatic amino developing agents used with the coupler compounds of our invention include the mono-, di-, and tri-amino aryl compounds and their derivatives formed by substitution in the amino group as Well as in the ring, such as alkyl, phenylene diamines and alkyl toluene diamines. These compounds are usually employed in the salt form, such as the hydrochloride or the sulfate which is more stable than the amines themselves. Suitable compounds are diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine sulfate, and 2 amino 5- diethylaminotoluene hydrochloride. The p-aminophenols and their substitution products may also be used where the amino group is unsubstituted. All of these developing agents have an unsubstituted amino group to which the oxidation products of the developer couple with the colorforming compounds to form dye images.

What I claim is:

1. A photographic silver halide emulsion containing as a color-forming coupler a compound having the general formula wherein R represents a mononuclear aryl group of the benzene series, and R represents a member of the group consisting of mononuclear aralkyl groups of the benzene series, mononuclear aryloxyalkyl groups of the benzene series, and mononuclear arylene groups of the benzene series.

2. A photographic silver halide emulsion containing as a color-forming coupler a compound having the general formula set forth in claim 1 wherein R represents a mononuclear aryl group of the benzene series and R represents a mononuclear arylene group of the benzene series.

3. A photographic silver halide emulsion containing as a color-forming coupler a compound having the general formula set forth in claim 1 wherein R and R each represent a mononuclear arylene group of the benzene series.

4. A photographic silver halide emulsion containing as a color-forming coupler the compound l-(2,4,6-trichloro phenyl) -3 -{moc- 2,4-di tert-amylphenoxy) -acetamido] benzamido}-S-m-sulfobenzoxy pyrazole pyridinium salt.

5. A photographic silver halide emulsion containing as a color-forming coupler the compound 1-phenyl-3-{m-[a- (2,4-di tert amylphenoxy)acetamido]benzamido}-5-m sulfobenzoxy pyrazole pyridinium salt.

6. A photographic silver halide emulsion containing as a color-forming coupler the compound l-lp-(p-tert-butylphenoxy)-phenyl]-3-[a-(p tert butylphenoxy) -propionamidol-S-m-sulfobenzoxy pyrazole pyridinium salt.

7. A photographic silver halide emulsion containing as a color-forming coupler the compound l-phenyl-3-{m-l'y- (2,4-di-tert amylphenoxy)butyramido]benzamido}-5-msulfobenzoxy pyrazole pyridinium salt.

8. A photographic silver halide emulsion containing as a color-forming coupler the compound 1-(2,4,6-trichlorophenyl)-3-{a-{p-[a-(2,4-di tert amylphenoxy)acetamido]phenyl}acetamido}-5-m sulfobenzoxy pyrazole pyridinium salt.

9. The method of producing a colored photographic image in a silver halide emulsion layer which comprises incorporating into said layer a coupler compound selected from those set forth in claim 1, exposing the emulsion layer to light and developing the emulsion layer with a primary aromatic amino silver halide developing agent, thereby forming a dye in the exposed region of the layer the pyrazolone nucleus of which contains only a carbonyl group in the 5-position.

References Cited in the file of this patent UNITED STATES PATENTS 2,369,489 Porter et al Feb. 13, 1945 2,436,130 Weissberger et al Feb. 17, 1948 2,476,986 Martin July 26, 1949 2,476,988 Martin July 26, 1949 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING AS A COLOR-FORMING COUPLER A COMPOUND HAVING THE GENERAL FORMULA 